CN102844397B

CN102844397B - Two-component structural adhesive which is impact resistant at room temperature

Info

Publication number: CN102844397B
Application number: CN201180019246.8A
Authority: CN
Inventors: K·福里克; J·芬特; A·克拉莫; U·格贝尔
Original assignee: Sika Technology AG
Current assignee: Sika Technology AG
Priority date: 2010-03-02
Filing date: 2011-03-01
Publication date: 2015-07-08
Anticipated expiration: 2031-03-01
Also published as: DK2542637T3; ES2677354T3; US9296931B2; EP2542637B1; WO2011107450A2; US20130230726A1; EP2365046A1; WO2011107450A3; CN102844397A; PL2542637T3; EP2542637A2; JP2013521362A; JP5916634B2

Abstract

The invention relates to the field of two-component epoxy resin compositions and to the use thereof as a repairing adhesive, in particular in vehicle construction. The two-component epoxy resin compositions according to the invention contain a curing component K2, which comprises between 1 and 10 wt.% of an amino group-terminated polyamide B, together with an epoxy resin component K1. The compositions are characterized in that the impact resistance is highly increased while an acceptable sheer strength is simultaneously retained.

Description

The two-component structure adhesive of the cured at room temperature of impelling strength

Technical field

The present invention relates to field of two-component epoxy resin, and relate to the purposes of described composition as maintenance tackiness agent, particularly in automobile making.

Background technology

At automobile and appurtenances or also have in the manufacture of machine and equipment and use high quality binder to replace more and more or in conjunction with traditional method of joining such as screw, rivet, punching or welding.To glued construction parts, the high strength of tackiness agent and impelling strength are most important.

In automobile making with established the thermosetting adhesive usually solidified at higher than 60 DEG C and sometimes up to the temperature of 170 DEG C in field of automobile repair.But their application is normally disadvantageous, such as when auto repair in the workshop without the equipment needed for thermofixation.In addition, the maintenance of automobile is---contrary with its manufacture---to be carried out on the automobile equipped completely, so that thermo-sensitive material also may be made to suffer damage.

Therefore, the tackiness agent that at room temperature can solidify, particularly bicomponent epoxy adhesive is significant.But they do not show the mechanical property identical with thermosetting adhesive usually, thus still there is the space of improving further.

Generally speaking, although epoxy adhesive is characterised in that high physical strength, particularly high tensile strength.But when adherend experiences a shock load, traditional epoxy adhesive is crossed crisp and can not be met the requirement of particularly automotive industry under therefore there is the impact conditions of high tensile loading and peel load wherein far away in most of situation.In this respect, at high temperature but especially also lower than under the low temperature of-10 DEG C, intensity is inadequate.

Therefore attempt by various method the impelling strength improving epoxy adhesive.

In the literature, substantially two kinds of methods that the fragility how reducing epoxy adhesive also improves impelling strength are thus proposed: on the one hand, by being added to the crosslinked macromolecular compound of small part, such as the latex of core/shell polymeric or other flexibilized polymkeric substance and multipolymer can realize this object.On the other hand, by introducing soft chain segment, such as, pass through correspondingly modified epoxy component and can realize toughness increase to a certain degree.

WO 2009/025991 A1 describes the epoxy resin binder for automobile making solidified at relatively low temperature.The disclosed two-component structure adhesive in there has three kinds of main ingredients, the rubber that polyethers, the uncle of 4-40 % by weight or secondary amino group that namely the uncle of 15-50 % by weight or secondary amino group stop stop; With 10-30 % by weight, there is the uncle of the melt temperature being no more than 50 DEG C or the polymeric amide of secondary amino group termination.In addition, said composition comprises at least one impelling strength improving agent in addition.

But described bi-component epoxide-resin composition has the impelling strength being still improved ability.

Invention describes

Therefore, the object of this invention is to provide the novel bi-component epoxide-resin composition that can increase impelling strength and keep acceptable tensile shear strength simultaneously.

Be surprisingly found out that novel bi-component epoxide-resin composition according to claim 1 overcomes the defect of prior art.

Even if composition epoxy resin according to the present invention is particularly suitable for wherein requiring adhering junction body under circumstances of high mechanical loads, such as, in accident situation, also keep the automobile making of their integrity.

Other side of the present invention is the theme of other independent claim.Particularly preferred embodiment is the theme of dependent claims.

Embodiments of the present invention

In first aspect, the present invention relates to a kind of bi-component epoxide-resin composition, comprise:

-comprising the epoxy resin ingredient K1 of at least one epoxy resin A, described epoxy resin per molecule has on average more than one epoxy group(ing);

With

-curing agent component K2, it comprises the total weight 1-10 % by weight based on curing agent component, the polymeric amide B of the amino termination of preferred 4-8 % by weight;

Wherein at least one of component K1, K2 comprises at least one impelling strength improving agent C.

Herein whole, such as, prefix " poly-(many) " representation in " polymeric amide ", " polyisocyanates ", " polyvalent alcohol " or " polyphenol " comprises the molecule of two or more each functional groups.

" impelling strength improving agent " refers to the additive in epoxy matrix material in the literature, even if it is when adding on a small quantity, when particularly adding 0.1-35 % by weight, preferred 0.5-15 % by weight, also make the toughness of solidifying rear matrix significantly increase, and therefore, it is possible to absorbed before matrix is torn or ruptured higher bending, stretch, impact or bump stroke.Generally speaking, the tolerance of impelling strength is made according to the impact peel function of ISO 11343.Here, energy-to-break (BE) is expressed as the area under experiment curv (from 25% to 90%, according to ISO 11343).Generally speaking, can measure as the another kind of impelling strength according to the impact peel strength of ISO 11343.

Term " polymer " in the literature " comprise on the one hand by polyreaction (poly-addition, addition polymerization, polycondensation) but prepare chemically evenly in the macromolecular set that the polymerization degree, molecular weight are different with chain long side.On the other hand, this term also comprises the derivative of the described macromole set obtained by polyreaction, namely obtained by the reaction such as addition or replacement of functional group on predetermined macromole and can chemical homogeneous or the uneven compound of chemistry.In addition, this term also comprises so-called prepolymer, i.e. reactive oligomeric pre-adducts, and its functional group participates in macromolecular structure.

In the literature, the use of the term " independently of one another " relevant from substituting group, residue or group will be interpreted as can occurring in same a part the substituting group of the same names simultaneously with different implication, residue or group.

The epoxy resin A that in epoxy resin ingredient K1, per molecule has an average more than one epoxy group(ing) is preferably liquid epoxies or solid epoxy.Term " solid epoxy " is that epoxide those skilled in the art are very known, and uses relative to " liquid epoxies ".The second-order transition temperature of solid resin is higher than room temperature, and namely they can at room temperature be ground into free-pouring powder.

Preferred solid epoxy has formula (IX)

In the formula, substituent R ' and R " be H or CH independently of one another separately ₃.In addition, index s has the value of >1.5, is in particular 2-12.

This solid epoxy can be such as commercially available by Dow or Huntsman or Hexion.

The compound with the formula of index s between 1-1.5 (IX) is generally referred to by those skilled in the art as semi-solid epoxy resin.For the present invention, regard them as solid resin equally.But preferred sense stricto epoxy resin, namely its Exponential s has the value of >1.5.

Preferred liquid epoxies has formula (X)

In the formula, substituent R " ' and R " " be H or CH independently of one another separately ₃.In addition, index r represents the value of 0-1.Preferably, r represents the value being less than 0.2.

Therefore these be preferably the diglycidylether (DGEBA) of dihydroxyphenyl propane, the diglycidylether (title " A/F " referred to herein as and be used as the acetone of reactant and the mixture of formaldehyde in its preparation) of Bisphenol F and dihydroxyphenyl propane/F.This liquid resin can such as conduct gY 250, pY 304, gY 282 (Huntsman) or D.E.R. ^tM331, or D.E.R. ^tM330 (Dow) or Epikote 828 (Hexion) obtain.

In addition, so-called phenolic varnish are suitable epoxy resin A.These have following formula especially:

and or CH ₂, R1=H or methyl, and z=0-7.

Especially, they are phenol or cresol novolak (R2=CH ₂).

These epoxy resin can with trade(brand)name EPN or ECN and 556 from Huntsman or with product line D.E.N. ^tMcommercially available from Dow Chemical.

Preferably, epoxy resin A is the liquid epoxies of formula (X).In even preferred embodiment, heat-curable epoxy resin compositions comprises the liquid epoxies of at least one formula (X) and the solid epoxy of at least one formula (IX).

The ratio of epoxy resin A is preferably 10-85 % by weight, is in particular 15-70 % by weight, is preferably 15-60 % by weight, based on the weighing scale of composition.

The curing agent component K2 of at least one for epoxy resin is comprised in addition according to composition of the present invention.This solidifying agent is preferably selected from the compound by the group of poly-(ethyleneimine), polyamidoamines amine, the amino butadiene/acrylonitrile copolymer that stops and polyamines.

Polyamines be in particular have be less than 500g/mol molecular weight polyoxyalkylene diamines ( d-230, Jeffamine D400, eDR-148), 4,7,10-trioxatridecane-1,13-diamines, 4,9-dioxa dodecane-1,12-diamines, ethylene diamine and/or 3 (4), 8 (9)-bis-(amino methyl) three ring [5.2.1.0 ^2,6] decane ( produced by Celanese Chemicals).

In one embodiment, curing agent component K2 comprises poly-(ethyleneimine) of at the most 20 % by weight in addition, based on the total weight of curing agent component.

Curing agent component K2 comprises 1-10 % by weight, the polymeric amide B that the amino between preferred 4-8 % by weight stops, based on the total weight of curing agent component.Scope between described 1-10% does not comprise corresponding extreme value, and namely 1 and 10 % by weight.If have been found that and exceed this ratio especially, then the impelling strength of the tackiness agent solidified significantly reduces.The ratio of the polymeric amide B that the amino from about 8 % by weight stops, selectively under test conditions the impelling strength of binder composition significantly deteriorated.Therefore have been found that, if binder composition comprises more than 8, particularly more than or equal 10 % by weight polymeric amide, then the impelling strength under 0 DEG C, 23 DEG C (respectively after 7 days) and 60 DEG C (distinguishing after 2 hours) significantly reduces (also see accompanying drawing ...).

Although in example described here, the increase of impelling strength reduces with the slightly relative of tensile shear strength and links together, but generally speaking can provide the two component adhesive composition with significantly improved overall performance.

Preferably, the amino polymeric amide B stopped is the polymeric amide that uncle or secondary amino group stop.

The preferred per molecule of polymeric amide comprises average at least 1.5, and especially preferably at least 1.8 and most preferably at least 2.0 uncles or secondary amino group.Typical example is per molecule 2-3 uncle or secondary amino group, but also can imagine per molecule 6 or more uncle or secondary amino group.

Especially preferred polymeric amide is the lipid acid of dimerization and the reaction product of polyamines.The example of this polymeric amide comprises can trade(brand)name 115, 125 Hes 140 obtain from Cognis company those.

In one embodiment, described composition comprises the polyurethane prepolymer by having isocyanate groups, the impelling strength improving agent C1 that the amino that primary diamines and optionally at least one Michael receptor response obtain stops is as impelling strength improving agent C, the polyurethane prepolymer wherein with isocyanate groups is had polyester or the polyether glycol preparation of at least two hydroxyls by least one polyisocyanates and at least one, and described impelling strength improving agent is a part of curing agent component K2, based on the weighing scale of curing agent component K2, it is in particular the amount of 1-30 % by weight.

Especially, diamines is selected from by the following group formed: the aliphatic diamine comprising ether, particularly polyoxyalkylene diamines, particularly polyethylene oxide diamines, polyoxypropylene diamine; Polyoxybutylene diamines, the polyhutadiene of amino termination and butadiene/acrylonitrile copolymer, or their mixture.

Especially, these are such as can title (from HuntsmanChemicals), with title Polyetheramin (from BASF) or with title PC what (from Nitroil) was commercially available have two amino polyoxyalkylene polyamines, and the mixture of above-mentioned polyamines.

Preferred diamines has two amino polyoxyalkylene polyamines, those of especially formula (VIIIa).

Here, g ' represents and represents structural unit derived from oxyethane derived from the structural unit of propylene oxide and h '.In addition, g, h and i represent the value of 0-40 separately, and condition is summation >=1 of g, h and i.Especially, the molecular weight of preferred 100-4,000g/mol.

Particularly preferred diamines be as by Huntsman Chemicals D series and ED series under provide those such as d-230, d-400, d-2000, d-4000, eD-600, eD-900 or eD-2003.

According to the present invention, the reaction process of preparation impelling strength improving agent C1 can be undertaken by several response path, and this refers to the polyurethane prepolymer and/or primary diamines with isocyanate groups and/or has and the polyurethane prepolymer of the isocyanate group of diamine reactant and Michael receptor response.

Therefore, the amino impelling strength improving agent stopped can be stopped by secondary amino group in one embodiment, and is obtained from the amino impelling strength improving agent of termination and the reaction of primary amino and Michael acceptor.

In one embodiment, impelling strength improving agent C1 used according to the invention is characterised in that in order to polyurethane preformed polymer, and at least one also can be used except at least one polyether glycol or polyester polyol to have the polymkeric substance Q of terminal amino group, thiol group or hydroxyl _pMand/or the polyphenol Q that at least one optionally replaces _pP.

The suitable polymkeric substance Q with terminal amino group, thiol group or hydroxyl _pMbe in particular the polymkeric substance Q with two or three terminal amino groups, thiol group or hydroxyl _pM.

Preferably, polymkeric substance Q _pMthere is 300-6,000, be in particular 600-4,000, the equivalent of preferred 700-2,200g/ equivalent NCO-reactive group.

Suitable polymkeric substance Q _pMpolyvalent alcohol, such as following commercially available polyvalent alcohol or their any mixture:

– polyoxyalkylene polyols, also polyether glycol or oligomeric ether alcohol is claimed, it is oxyethane, 1, 2-propylene oxide, 1, 2-or 2, 3-butylene oxide ring, trimethylene oxide, the polymerisate of tetrahydrofuran (THF) or its mixture, and be optionally polymerized by means of the starter molecules with two or more reactive hydrogen atoms, described starter molecules such as water, ammonia or there is the compound such as 1 of multiple OH or NH group, 2-ethylene glycol, 1, 2-and 1, ammediol, neopentyl glycol, Diethylene Glycol, triethylene glycol, the dipropylene glycol of isomery and tripropylene glycol, the butyleneglycol of isomery, pentanediol, hexylene glycol, heptanediol, ethohexadiol, nonanediol, decanediol, undecane, 1, 3-and 1, 4-cyclohexanedimethanol, dihydroxyphenyl propane, Hydrogenated Bisphenol A, 1, 1, 1-trimethylolethane, 1, 1, 1-TriMethylolPropane(TMP), glycerine, the mixture of aniline and above-claimed cpd.Can use and there is low-unsaturation-degree (measure according to ASTM D-2849-69 and represent with the milliequivalent degree of unsaturation (mEq/g) of every gram of polyvalent alcohol) and such as use polyoxyalkylene polyols prepared by so-called bimetallic cyanide complex catalyst (dmc catalyst), and there is higher degree of unsaturation and such as use the polyoxyalkylene polyols that anionic catalyst is prepared as NaOH, KOH, CsOH or alkali metal alcoholates.

Especially it is suitable that polyoxyalkylene glycol or polyoxyalkylene triol, particularly oxide glycols or polyoxypropylene triol.Especially be applicable to be there is the degree of unsaturation that is less than 0.02mEq/g and molecular weight at the polyoxyalkylene glycol of 1,000-30,000g/mol scope and triol, and molecular weight is oxide glycols and the triol of 400-8,000g/mol.

(" EO-end-blocking ", ethylene oxide-capped) polyoxypropylene polyol that so-called oxyethane stops is suitable equally.The latter is special polyoxypropylene-polyethylene oxide-polyvalent alcohol, it can such as obtain like this: after the poly-propoxylation with oxyethane reacts and terminates, and pure polyoxypropylene polyol, particularly oxide glycols and the further alkoxylate of triol are made it have primary hydroxyl thus.

In addition, the compound exemplified is:

The polybutadiene polyol that-hydroxyl stops, such as, by 1,3-butadiene and allyl alcohol polymer or by obtained those of polyhutadiene oxidation, and their hydrogenated products;

The polyether glycol of-styrene-acrylonitrile or the grafting of acrylonitrile-methacylate methyl esters, particularly such as by Elastogran with trade(brand)name there is provided those;

– polyester polyol, also referred to as oligomer ester alcohol, its such as by two to trivalent alcohol as 1, 2-ethylene glycol, Diethylene Glycol, 1, 2-propylene glycol, dipropylene glycol, 1, 4-butyleneglycol, 1, 5-pentanediol, 1, 6-hexylene glycol, neopentyl glycol, glycerine, 1, 1, the mixture of 1-TriMethylolPropane(TMP) or aforementioned alcohol, with organic dicarboxylic acid or their acid anhydrides or ester such as succsinic acid, pentanedioic acid, hexanodioic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, toxilic acid, fumaric acid, phthalic acid, m-phthalic acid, prepared by the mixture of terephthalic acid and hexahydrophthalic acid or aforementioned acid, and the polyester polyol to be formed by lactone such as 6-caprolactone.

– polycarbonate polyol, as by above-mentioned alcohol for building polyester polyol and dialkyl carbonate, diaryl carbonate or phosgene be obtained by reacting those.

– polyacrylate polyol and polymethacrylate polyols.

The fat of – poly-hydroxy official energy and oil, such as natural fat and oil, particularly Viscotrol C; Or by the polyvalent alcohol of polyvalent alcohol-so-called oil chemistry that chemical modification natural fat and oil obtain, such as, by epoxidation unsaturated oil and the epoxy polyester obtained with carboxylic acid or alcohol open loop subsequently or epoxidized polyether; Or by the polyvalent alcohol that hydroformylation and the hydrogenation of unsaturated oil obtain; Or by natural fat and oil by degradation process as alcoholysis or ozone decomposed and chemical bonding subsequently, the polyvalent alcohol such as obtained by the transesterify of degraded product or derivatives thereof that so obtains or dimerization.Degraded product particularly lipid acid and fatty alcohol and the fatty acid ester, particularly methyl ester (FAME) of the natural fat be applicable to and oil, it such as and can be hydrogenated to hydroxy fatty acid and be derivatized by hydroformylation.

– gathers hydrocarbon polyvalent alcohol, also referred to as oligomeric hydrocarbon alcohol, as such as poly-hydroxy official can ethylene-propylene, Ethylene/Butylene or ethylene-propylene-diene copolymer, they are such as produced by Kraton Polymers company, or be obtained from diene as 1,3-divinyl or diene mixture and vinyl monomer as the poly-hydroxy official of vinylbenzene, vinyl cyanide or iso-butylene can multipolymer, or the polybutadiene polyol of poly-hydroxy official energy, such as obtained by the copolymerization of 1,3-butadiene and vinyl carbinol and also can be hydrogenated those.

-poly-hydroxy official can acrylonitrile butadiene copolymer, the acrylonitrile butadiene copolymer as such as stopped by epoxide or amino alcohol and carboxyl (commercial can trade(brand)name Hypro ^tM(be in the past ) CTBN and CTBNX by Nanoresins AG(Germany) or Emerald Performance Materials LLC obtains) obtain those.

-there is the amphipathic nature block polymer of at least one hydroxyl.

In the literature, be interpreted as the amphipathic nature block polymer with at least one hydroxyl and comprise at least one and the blendable block of epoxy resin, and the multipolymer of at least one and the immiscible block of epoxy resin.Especially, amphipathic nature block polymer is that their content is hereby incorporated by as being disclosed in those in A1 of WO 2006/052725 A1, WO 2006/052726 A1, WO 2006/052727 A1, WO 2006/052728A1, WO 2006/052729 A1, WO 2006/052730 A1, WO 2005/097893.

With example particularly polyethylene oxide, poly(propylene oxide), poly-(oxyethane-altogether-propylene oxide) and poly-(oxyethane-ran-propylene oxide) block and composition thereof of the blendable block of epoxy resin.

With the example of the immiscible block of epoxy resin, the polyether block particularly prepared by the epoxy alkane with at least 4 carbon atoms on the one hand, the preferred butylene oxide ring of described epoxy alkane, oxepane and/or Epoxydodecane.Particularly preferably as this polyether block is polybutylene oxide, poly-oxepane and poly-Epoxydodecane block and composition thereof.

Polyethylene, polyethylene propylene, polyhutadiene, polyisoprene, polydimethylsiloxane and polyalkyl methacrylate block and composition thereof on the other hand with the example of the immiscible block of epoxy resin.

In one embodiment, the amphipathic nature block polymer with at least one hydroxyl is the segmented copolymer that the other epoxy alkane with at least 4 carbon atoms of oxyethane and/or propylene oxide and at least one is formed, and described epoxy alkane is preferably from the group of butylene oxide ring, oxepane and Epoxydodecane composition.

In another preferred embodiment, the amphipathic nature block polymer with at least one hydroxyl is selected from by poly-(isoprene-block-oxyethane) segmented copolymer (PI-b-PEO), poly-(ethylene, propylene-b-oxyethane) segmented copolymer (PEP-b-PEO), poly-(divinyl-b-oxyethane) segmented copolymer (PB-b-PEO), poly-(isoprene-b-oxyethane-b-isoprene) segmented copolymer (PI-b-PEO-PI), the group that poly-(isoprene-b-oxyethane-methyl methacrylate) segmented copolymer (PI-b-PEO-b-PMMA) and poly-(ethene-alt-propylene) segmented copolymer (PEO-PEP) of poly-(oxyethane)-b-form.

Especially, amphipathic nature block polymer can diblock, three blocks or four block form exist.For many blocks, i.e. particularly three or four blocks, these with straight chain or branched chain, can exist particularly as starblock.

The preparation of amphipathic nature block polymer is that those skilled in the art are such as from Macromolecules 1996,29,6994 – 7002 and Macromolecules 2000,33,9522 – 9534 and J.Polym.Sci.Part B:Polym.Phys.2007, known in 45,3338 – 3348, their content is hereby incorporated by.Described amphipathic nature block polymer has at least one hydroxyl.Depend on preparation method, amphipathic nature block polymer can have one or more hydroxyl.

If the polymerization of such as epoxy alkane uses methyl alcohol initial and stops with acid, then produce the amphipathic nature block polymer with hydroxyl.

If started with glycol such as ethylene glycol on the contrary, then produce the amphipathic nature block polymer with two hydroxyls.

If use the alcohol with three, four or more hydroxyl as initiator, then correspondingly produce the amphipathic nature block polymer with three, four or more hydroxyl.

Described preparation can such as be carried out in continuous synthesis technique, wherein first by the auxiliary lower polymerization of the first monomer such as butylene oxide ring at initiator, then add the second monomer such as oxyethane, it will be aggregated in the polymer ends of the first formed monomer.Thus, can such as use single methanol as poly-(butylene oxide ring) (PEO-PBO) amphiphilic diblock copolymer of poly-(the oxyethane)-b-of initiator preparation.Dibasic alcohol is such as used to form poly-(oxyethane)-b-poly-(butylene oxide ring)-poly-(oxyethane) (PEO-PBO-PEO) amphipathic three block copolymer.

But, also can first by the auxiliary lower polymerization of the first monomer such as butylene oxide ring at initiator, then add the mixture of two or more monomers, the mixture of such as oxyethane and butylene oxide ring, it will be aggregated in the polymer ends of the first formed monomer.Thus, can preparation example as poly-(ethylene oxide/butylene oxide)-poly-(butylene oxide ring)-poly-(ethylene oxide/butylene oxide) (PEO/BO-PBO-PEO/BO) amphipathic nature block polymer.

As the example of this amphipathic nature block polymer with at least one hydroxyl, the Fortegra deriving from Dow Chemical can be mentioned ^tM100.

Except the polyvalent alcohol that these are mentioned, polymkeric substance Q can also prepared _pMin and with a small amount of low-molecular-weight dibasic alcohol or polyvalent alcohol, such as 1, 2-ethylene glycol, 1, 2-and 1, ammediol, neopentyl glycol, Diethylene Glycol, triethylene glycol, the dipropylene glycol of isomery and tripropylene glycol, the butyleneglycol of isomery, pentanediol, hexylene glycol, heptanediol, ethohexadiol, nonanediol, decanediol, undecane, 1, 3-and 1, 4-cyclohexanedimethanol, Hydrogenated Bisphenol A, dimer fatty alcohol, 1, 1, 1-trimethylolethane, 1, 1, 1-TriMethylolPropane(TMP), glycerine, tetramethylolmethane, sugar alcohol is as Xylitol, Sorbitol Powder or N.F,USP MANNITOL, sugar is as sucrose, other are polyvalent alcohol more, the lower molecular weight alkoxylated polymerization product of aforementioned dibasic alcohol and polyvalent alcohol, and the mixture of aforementioned alcohols.Equally, also can be used together the polyvalent alcohol that a small amount of having is greater than the average OH functionality of 3, such as sugar polyol.

Described polymkeric substance Q _pMpreferably there are 300 to 6,000g/OH equivalents, be in particular 600 to 4,000g/OH equivalents, be preferably two senses of OH equivalent weight or the polyvalent alcohol of higher functional of 700 to 2,200g/OH equivalents.In addition, polyvalent alcohol is preferably selected from by polyoxyethylene glycol, polypropylene glycol, PLURONIC F-127, polytetramethylene glycol, the polyhutadiene that hydroxyl stops, the butadiene/acrylonitrile copolymer that hydroxyl stops, the synthetic rubber that hydroxyl stops, the group of the mixture composition of their hydrogenated products and polyvalent alcohol described in these.

For some application, suitable polymkeric substance Q _pMbe in particular the reaction product of the polyhutadiene or polyisoprene with hydroxyl or its partially or completely hydrogenation.

In addition, as polymkeric substance Q _pMcan also use the polyvinyl ether that the amino of two senses or higher functional stops, polypropylene ether is such as with trade(brand)name by commercially available those of Huntsman, polybutene ether, polyhutadiene, butadiene/acrylonitrile copolymer, such as, with trade(brand)name Hypro ^tM(be in the past ) ATBN is by Nanoresins AG(Germany) or commercially available those of Emerald Performance Materials LLC, and mixtures of other amino synthetic rubber of stopping or described component.

Also hydroxyl, sulfydryl or the amino polysiloxane stopped can be used as polymkeric substance Q _pM.

In addition, polymkeric substance Q _pMalso can carry out chainpropagation, this can carry out with the reaction of method by polyamine, polyvalent alcohol and polyisocyanates, particularly diamines, glycol and vulcabond in the manner known to persons skilled in the art.

Especially, glycol and/or diamines and vulcabond are preferred for chainpropagation.Certainly it will be apparent for a person skilled in the art that the polyhydric alcohols of higher functional is as TriMethylolPropane(TMP) or tetramethylolmethane, or the isocyanuric acid ester of the polyisocyanates of higher functional as vulcabond also may be used for chainpropagation.

Usually for polyether polyols with reduced unsaturation and the polyether polyols with reduced unsaturation in particular for chainpropagation, advantageously notice that described polymkeric substance does not have too high viscosity, if when particularly the compound of higher functional being used for chainpropagation.

Preferred polymkeric substance Q _pMbe the polyvalent alcohol with 600 to 6000 daltonian molecular weight, it is selected from by polyoxyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol block polymkeric substance, polytetramethylene glycol, the polyhutadiene that hydroxyl stops, the group of the perbutan that hydroxyl stops and their mixture composition.

Particularly preferred polymkeric substance Q _pMwhat stopped by amino, mercaptan or preferred hydroxyl has C ₂-C ₆the C of alkylidene group or mixing ₂-C ₆the α of alkylidene group, alpha, omega-dihydroxy polyalkylene glycol, or polyhutadiene or the polyisoprene with hydroxyl, or the reaction product of its part or all of hydrogenation.

As polyphenol Q _pPit is particularly suitable that dihydric phenol, trihydric phenol and tetrahydric phenol.This not only refers to pure phenol, and optionally also has the phenol replaced.The type replaced can be multiple.Particularly, this is interpreted as the replacement on the aromatic nucleus that directly connects at phenolic hydroxyl group.In addition, " phenol " not only refers to monokaryon aromatic substance, and aromatics that is that also refer to multinuclear or that condense or heteroaromatics, they have the phenolic hydroxyl group be directly connected on aromatic substance or heteroaromatics.

Dihydric phenol and trihydric phenol are particularly suitable.Such as, suitable dihydric phenol or trihydric phenol are Isosorbide-5-Nitrae-dihydroxy-benzene, 1,3-dihydroxy-benzene, 1,2-dihydroxy-benzene, 1,3-orcin, 3,5-resorcylic acid ester, two (4-hydroxy phenyl) propane (=dihydroxyphenyl propane) of 2,2-, two (4-hydroxy phenyl) methane (=Bisphenol F), two (4-hydroxy phenyl) sulfone (=bisphenol S), naphthoresorcinol, dihydroxy naphthlene, dihydroxyanthraquinone, dihydroxybiphenyl, two (p-hydroxybenzene) phthalide of 3,3-, 5,5-two (4-hydroxy phenyl) six hydrogen-4,7-endo-methylene group indane, phenolphthalein, fluorescein, 4,4'-[two (hydroxy phenyl)-1,3-phenylene two (1-methyl ethylidene)] (=bis-phenol M), 4,4'-[two (hydroxy phenyl)-Isosorbide-5-Nitrae-phenylene two (1-methyl ethylidene)] (=bis-phenol P), 2,2'-diallyl bisphenol, the dihydric phenol and xylenol prepared is reacted by phenol or cresols and two isopropylidene benzene, Phloroglucinol, gallic acid ester, there are the phenol novolacs of the OH-functionality of 2.0 to 3.5 or whole isomer of cresol novolak and above-claimed cpd.

Reacting the preferred dihydric phenol prepared and xylenol by phenol or cresols and two isopropylidene benzene has as correspondingly for the chemical structural formula that cresols illustrates as an example as follows:

Particularly preferably be the bis-phenol of difficult volatilization.Bis-phenol M, bis-phenol-S and 2,2'-diallyl bisphenol are considered to most preferred.

Q _pPpreferably there are 2 or 3 phenolic group.

Use at least one polyisocyanates for the preparation of polyurethane prepolymer.For polyisocyanates particularly vulcabond or the triisocyanate of this object.

Aliphatic series, cyclic aliphatic or aromatic polyisocyanate, particularly vulcabond can be used as polyisocyanates.Specially suitable be following these:

– 1,6-hexamethylene diisocyanate (HDI), 2-methyl pentamethylene-1,5-vulcabond, 2,2,4-and 2,4,4-trimethylammonium-1,6-hexamethylene diisocyanate (TMDI), 1,10-decamethylene vulcabond, 1,12-ten dimethylene diisocyanate, Methionin and Methionin ester vulcabond, hexanaphthene-1,3-and-1, any mixture (HTDI or H of any mixture of 4-vulcabond and these isomer, 1-methyl-2,4-and-2,6-bis-isocyanatocyclohexane and these isomer ₆tDI), 1-isocyanato-3,3,5-trimethylammonium-5-isocyanato methylcyclohexane (=isophorone diisocyanate or IPDI), perhydro--carotene 2,4'-and-4,4'-diphenylmethanediisocyanate (HMDI or H ₁₂mDI), 1,4-bis-isocyanato-2,2,6-trimethyl-cyclohexane (TMCDI), 1,3-and 1,4-is two-(isocyanatomethyl) hexanaphthene, m-and p-eylylene diisocyanate (m-and p-XDI), m-and p-tetramethyl--1,3-with-Isosorbide-5-Nitrae-eylylene diisocyanate (m-and p-TMXDI), two-(1-isocyanato-1-methylethyl)-naphthalene.

– 2,4-and 2, the any mixture (TDI), 4 of 6-inferior cresyl vulcabond and these isomer, 4'-, 2,4'-and 2, the any mixture (MDI), 1 of 2'-diphenylmethanediisocyanate and these isomer, 3-and Isosorbide-5-Nitrae-phenylene vulcabond, 2,3,5,6-tetramethyl--Isosorbide-5-Nitrae-two isocyanato-benzene, naphthalene-1,5-vulcabond (NDI), 3,3'-dimethyl-4,4'-bis-isocyanato-biphenyl (TODI), dianisidine diisocyanate (DADI).

The oligopolymer (such as biuret, isocyanuric acid ester) of the above-mentioned monomeric diisocyanate of – and polymkeric substance.

Any mixture of the above-mentioned polyisocyanates of –.

Preferably monomeric diisocyanate, particularly MDI, TDI, HDI and IPDI.

In one embodiment, the Michael acceptor being suitable for preparing impelling strength improving agent C1 used according to the invention has formula (I) or (Ia)

Wherein

R ⁴be hydrogen atom or be selected from by-R ⁷,-COOR ⁷the group of the group that He – CN forms,

And R ⁵be selected from by-COOR ⁷,-CONH ₂,-CONHR ⁷,-CONR ⁷ ₂,-CN ,-NO ₂,-PO (OR ⁷) ₂,-SO ₂r ⁷with-SO ₂oR ⁷the group of the group of composition, and

R ⁶be hydrogen atom or be selected from by-CH ₃,-R ⁷,-COOR ⁷with-CH ₂cOOR ⁷the group of the group of composition,

Wherein R ⁷it is the monovalent hydrocarbon group with 1-20 carbon atom.

In another embodiment, the Michael acceptor reacted with the polyurethane prepolymer with isocyanate groups has hydroxyl.

According to the present invention, the Michael acceptor with hydroxyl has formula (VII) or (VIIa) especially.

Wherein

R ⁴' be hydrogen atom or be selected from by-R ⁷,-COOR ⁷the group of the group that He – CN forms,

R ⁵' be selected from by-COOR ⁷,-CONH ₂,-CONHR ⁷,-CONR ⁷ ₂,-CN ,-NO ₂,-PO (OR ⁷) ₂,-SO ₂r ⁷with-SO ₂oR ⁷the group of the group of composition, and

R ⁶' be hydrogen atom or be selected from by-R ⁷,-COOR ⁷,-CH ₂cOOR ⁷the group of the group that He – CN forms,

Wherein R ⁷it is the monovalent hydrocarbon group with 1-20 carbon atom;

Y ⁴be the alkylidene group with 1-6 carbon atom, or do not exist under the prerequisite of p and p'=0; With

P represents 0 or 1.

The particularly preferably embodiment of the compound of formula (VII) and (VIIa) is those compounds: wherein Y ⁴for without and p is 0 (vinyl alcohol); Y ⁴for CH ₂and p is 0 (vinyl carbinol); Y ⁴for CH ₂cH ₂and p is 1, R ⁴' be H or CH ₃((methyl) Hydroxyethyl Acrylate (HEA) (HEMA)); Y ⁴for propylidene and p is 1, R ⁴' be H or CH ₃((methyl) hydroxypropyl acrylate (HPA) (HPMA)); Y ⁴for butylidene, p is 1, R ⁴' be H or CH ₃((methyl) hydroxy butyl acrylate).

The example of suitable Michael acceptor is maleic acid diester or dimethyl ester, such as dimethyl maleate, ethyl maleate, dibutyl maleinate, DEF; Diesters is citraconic acid dimethyl ester such as; Acrylic or methacrylic acid esters is (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) vinylformic acid tetrahydrofuran ester, (methyl) isobornyl acrylate such as; Acrylamide or Methacrylamide be (methyl) acrylamide, methyl (methyl) acrylamide, butyl (methyl) acrylamide, dimethyl (methyl) acrylamide, dibutyl (methyl) acrylamide such as; Methylene-succinic acid diester such as dimethyl itaconate; Laurate is methyl cinnamate such as; Vinyl phosphonic acid diesters is vinyl phosphonic dimethyl phthalate such as; Vinyl sulfonic acid ester, particularly vinyl sulfonic acid aromatic ester; Vinyl sulphone; Vinyl nitrile is vinyl cyanide, crotononitrile, 2-pentenenitrile or flumaronitrile such as; 1-nitroethylene such as beta-nitrostyrene; With Knoevenagel condensation product, such as formed by diester malonate and aldehyde such as formaldehyde, acetaldehyde or phenyl aldehyde those.Especially it is suitable that maleic acid diester, (methyl) acrylate, (methyl) acrylamide, phosphonic acid diester and vinyl nitrile.

Preferred Michael acceptor is dimethyl maleate, ethyl maleate and dibutyl maleinate, (methyl) tetrahydrofurfuryl acrylate, (methyl) isobornyl acrylate, (methyl) Ethyl acrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) 2-Hydroxy ethyl acrylate and (methyl) vinylformic acid-3-hydroxy propyl ester, (methyl) acrylamide, N-methyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, dimethyl phosphonate, diethyl phosphonate and aminophon, vinyl cyanide, 2-pentenenitrile, flumaronitrile and beta-nitrostyrene, and the mixture of these compounds.

In one embodiment, impelling strength improving agent C1 used according to the invention has general formula (II)

Wherein Y ¹it is the polyurethane prepolymer of the straight chain stopped by the individual isocyanate groups of m+m ' after removing all terminal isocyanate group group or branching;

Y ²that there is C ₂-C ₆the polyoxyalkylene of alkylidene group, polyhutadiene, butadiene/acrylonitrile copolymer or elastomeric divalent group;

Y ³the group of H or the alkyl with 1-10 carbon atom or formula (III) independently of one another,

Wherein

R ⁴be hydrogen atom or be selected from by-R ⁷,-COOR ⁷the group of He – CN composition group, and

R ⁵be selected from by-COOR ⁷,-CONH ₂,-CONHR ₇,-CONR ⁷ ₂,-CN ,-NO ₂,-PO (OR ⁷) ₂,-SO ₂r ⁷with-SO ₂oR ⁷the group of the group of composition, and

R ⁶be hydrogen atom or be selected from by-R ⁷,-COOR ⁷,-CH ₂cOOR ⁷the group of the group that He – CN forms,

Wherein R ⁷it is the univalence hydrocarbyl with 1-20 carbon atom;

Y ⁴be the alkylidene group with 1-6 carbon atom, or do not exist under the condition of p and p'=0; With

Y ⁵it is the divalent group of formula (IV) or (IV ');

Wherein

R ⁴' be hydrogen atom or be selected from by-R ⁷,-COOR ⁷the group of He – CN composition group, and

Wherein R ⁷it is the monovalent hydrocarbon group with 1-20 carbon atom;

P and p ' is 0 or 1 separately;

Q and q ' is 0 or 1 separately;

M and m ' is separately the value of 0-7, preferably 0 or 1 or 2, and condition is the value that m+m ' is 1-8, is in particular 1 or 2.

If q and q '=0, then formula (II) simplifies an accepted way of doing sth (V), namely

Wherein Y ¹the straight chain stopped by the individual isocyanate groups of m+m ' after being removing all terminal isocyanate groups group or the polyurethane prepolymer of branching;

Y ³the group of H or the alkyl with 1-10 carbon atom or formula (VI) independently of one another,

Wherein

R ⁵be selected from by-COOR ⁷,-CONH ₂,-CONHR ⁷,-CONR ⁷ ₂,-CN ,-NO ₂,-PO (OR ⁷) ₂,-SO ₂r ⁷with-SO ₂oR ⁷the group of the group of composition, and

Wherein R ⁷it is the monovalent hydrocarbon group with 1-20 carbon atom;

Dotted line in the structural formula of the literature represents the key between corresponding substituting group and affiliated molecule residues in each case.

In another embodiment, the feature of impelling strength improving agent C1 is, with primary diamines and the subsequently optional and Michael acceptor further by the reaction product that obtained by the polyurethane prepolymer and Michael receptor response with isocyanate groups, or with by and the secondary diamine prepared of the reaction of Michael acceptor react, wherein said primary diamines has 100-4,000g/mol, preferred 400-3,000g/mol, the particularly preferably molecular weight of 600-2,200g/mol.

In second aspect, the present invention relates to the polyurethane prepolymer by making to have isocyanate groups, the impelling strength improving agent that amino prepared by primary diamines and optionally at least one Michael receptor response stops, the polyurethane prepolymer wherein with isocyanate groups is had polyester polyol or the polyether glycol preparation of at least two hydroxyls by least one polyisocyanates and at least one, condition is if primary diamines has the molecular weight being less than 600g/mol, then Michael acceptor must be had to participate in the preparation of the impelling strength improving agent of amino termination, and compared with the polyurethane prepolymer with isocyanate groups, primary diamines is less than 0.5 use to make isocyanate groups with amino ratio.

Especially, isocyanate groups is less than 0.4 with amino ratio, is preferably less than 0.25.

The following describes the method preparing impelling strength improving agent C1.According to the present invention, the amino impelling strength improving agent C1 stopped is by making to have the polyurethane prepolymer of isocyanate groups, primary diamines and optionally at least one Michael receptor response and preparing.Many possibilities of reaction sequence and products therefrom are thus obtained at this.

In order to further illustrate the synthesis of impelling strength improving agent C1, find that following response path is favourable especially:

Reaction formula I:

According to reaction formula I, first the polyurethane prepolymer with isocyanate groups of the primary diamines of formula (VIII) and formula (XII) is reacted, the impelling strength improving agent that the amino according to the present invention obtaining formula (Va) stops.In this case, the amino impelling strength improving agent stopped has primary amino.

Here, the amount that the diamines of formula (VIII) is stoichiometrically excessive uses, especially with the polyurethane prepolymer NH relative to formula (XII) ₂group and the ratio of NCO group are greater than 2, are greater than 2.5 especially, the amount of 4 that is preferably greater than uses.This guarantees reliably to form simple adducts and prevents from being formed the oligomeric adduct of higher molecular.

Alternatively, primary diamines (VIII) and the Michael receptor response of formula (I) are obtained the secondary amine of formula (XIII) in the first reactions steps.Depend on the stoichiometric ratio of primary diamines (VIII) relative to the Michael acceptor of formula (I), the R in formula (XIII) and formula (IIb) represents the substituting group of H or formula (VI).In further step, the polyurethane prepolymer with isocyanate groups of the secondary amine of formula (XIII) and formula (XII) can be reacted, the impelling strength improving agent that the amino according to the present invention obtaining formula (II b) stops.In this case, the amino impelling strength improving agent stopped has secondary amino group.

But alternatively, also by formula, (the Michael receptor response of V impelling strength improving agent a) and formula (I) obtains the impelling strength improving agent that stops of the amino of this formula (II b).Here, depend on the consumption of the Michael acceptor of formula (I), obtain formula (II a) or (II b) amino stop impelling strength improving agent.In the first situation, the amino impelling strength improving agent stopped has primary and secondary amino; In a rear situation Chinese style, (two primary aminos of the impelling strength improving agent that V amino a) stops generate secondary amino group by Michael receptor response.

Reaction formula II:

If use the Michael acceptor of hydroxyl as Michael acceptor, then carry out new production path.This response path is described according to the Michael acceptor of the hydroxyl of formula (VII) especially in reaction formula II and III.

According to reaction formula II, by the polyurethane prepolymer with isocyanate groups of formula (XII) and the Michael receptor response according to the hydroxyl of formula (VII).If be selected as making the ratio with the isocyanate groups number of the polyurethane prepolymer of isocyanate groups of the hydroxy number of Michael acceptor and formula (XII) to be 0.5 at this according to the amount of the Michael acceptor of the hydroxyl of formula (VII), then this reaction will quantitatively obtain the intermediate product comprising isocyanate groups of formula (XIV), adds the primary diamines (excessive) of formula (VIII) in reactions steps subsequently wherein.How to add to according to this diamines in the double bond of intermediate product of formula (XIV) respectively, formed in the reaction formula (II c-1) or formula (II c-2) according to impelling strength improving agent of the present invention.

Reaction formula III:

Compare or the quantitative response (namely the hydroxy number of Michael acceptor and the ratio with the isocyanate groups number of the polyurethane prepolymer of isocyanate groups of formula (XII) have >=value of 1) of stoichiometric excess if the Michael acceptor according to the hydroxyl of formula (VII) and the polyurethane prepolymer with isocyanate groups according to formula (XII) measures according to the Michael receptor chemistry relative to hydroxyl, then quantitatively form the intermediate product according to formula (XV), as shown in reaction formula III.

In another reactions steps, will react according to the primary diamines of the intermediate product of formula (XV) and formula (VIII) according to reaction formula III.How to add to according to this diamines in the double bond of intermediate product of formula (XV) respectively, formed in the reaction formula (II d-1) or formula (II d-2) according to impelling strength improving agent of the present invention.

It will be apparent to one skilled in the art that, if the polyurethane prepolymer with isocyanate groups of the Michael acceptor of the hydroxyl of formula (VII) and formula (XII) with make the ratio with the isocyanate groups number of the polyurethane prepolymer of isocyanate groups of the hydroxy number of Michael acceptor and formula (XII) have the value of 0.5-1 mode and in reacting, then form the mixture of the reaction product of the formula (XIV) as shown in reaction formula II and the reaction product (XV) as shown in reaction formula III, then make after the primary diamines with formula (VIII) reacts further the formula that formed (II c-1) according to impelling strength improving agent of the present invention, or (depending on how diamines adds in the double bond of intermediate product respectively) formula (II c-2) and formula (II d-1) according to impelling strength improving agent of the present invention, or the mixture according to impelling strength improving agent of the present invention of (how adding in the double bond of intermediate product according to diamines respectively) formula (II d-2).

By it should be noted that be the preferred embodiment of Michael acceptor according to the Michael acceptor of formula (VII), i.e. the Michael acceptor of hydroxyl.Therefore, the possibility of the polyurethane prepolymer direct reaction realizing Michael acceptor and there is isocyanate groups is provided by the synthesis path as shown in reaction formula III, this especially show with according to the synthesis path of reaction formula I comparatively speaking, the structural unit deriving from Michael acceptor is combined in the main polymer chain (polymer backbone) of the amino impelling strength improving agent stopped with the distance larger from polymer ends.

In one embodiment, bi-component epoxide-resin composition comprises fluid rubber C2, described fluid rubber comprises the polymkeric substance that epoxy stops, the particularly acrylonitrile/butadiene multipolymer of epoxy termination, and be a part of epoxy resin ingredient K1, its weighing scale based on epoxy resin ingredient K1 is in particular the amount of 1-45 % by weight.

In another embodiment, impelling strength improving agent is the polymkeric substance C3 of formula (XI)

In the formula, the value of n and n ' each 0-7 naturally independently of one another, preferably 0 or 1 or 2, the value of condition to be n+n ' be 1-8, is in particular 1 or 2.

In addition, R ¹it is the polyurethane prepolymer of the straight chain stopped by the individual isocyanate groups of n+n ' after removing all terminal isocyanate group group or branching.

R ²and R ³represent independently of one another separately and be selected from by the substituting group of the following group formed

Here, R ¹⁴itself be the group of the aliphatic series comprising uncle or secondary hydroxyl, cyclic aliphatic, aromatics or the araliphatic epoxide after removing hydroxyl or epoxy group(ing), and pp represent the value of 1,2 or 3.

In the literature, " araliphatic groups " is interpreted as aralkyl, the alkyl that namely replaced by aryl (see cD chemie Lexikon, Version 1, Stuttgart/NewYork, Georg Thieme Verlag 1995).

In addition, R ¹⁵, R ¹⁶, R ¹⁷and R ¹⁸represent separately alkyl or cycloalkyl or aralkyl or aromatic yl alkyl group independently of one another, or R ¹⁵with R ¹⁶together, or R ¹⁷with R ¹⁸form a part for optional 4 to 7 rings replaced together.

In addition, R ¹⁹, R ¹⁹' and R ²⁰represent separately alkyl or aralkyl or aromatic yl alkyl group independently of one another, or alkoxyl group or aryloxy or aralkoxy, and R ¹¹represent alkyl.

R ²³and R ²⁴represent the alkylidene group with 2-5 carbon atom that optionally there is double bond or be substituted independently of one another separately, or the phenylene of phenylene or hydrogenation, and R ²⁵, R ²⁶and R ²⁷represent separately H or alkyl or aryl or aromatic alkyl group independently of one another.

Finally, R ²⁸represent aralkyl or optionally there is the monokaryon of aromatic hydroxy or multinuclear is that replace or unsubstituted aromatic compound moieties.

On the one hand, phenol or bis-phenol are counted as R especially after removing hydroxyl ²⁸.Especially, phenol, dihydroxyphenyl propane, Bisphenol F and 2 that phenol, cresols, Resorcinol, pyrocatechol, cardanol (3-15 carbene base phenol (deriving from cashew nut shell oil)), nonyl phenol, warp react with vinylbenzene or Dicyclopentadiene (DCPD), 2 '-diallyl bisphenol is the preferred example of this phenol and bis-phenol.

On the other hand, hydroxy-benzyl alcohol and benzylalcohol are counted as R especially after removing hydroxyl ²⁸.

If R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ¹⁹', R ²⁰, R ²¹, R ²⁵, R ²⁶or R ²⁷represent alkyl, then it is in particular the C of straight chain or branching ₁-C ₂₀alkyl.

If R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ¹⁹', R ²⁰, R ²⁵, R ²⁶, R ²⁷or R ²⁸represent aralkyl, then this group is in particular the aromatic group by methylene radical keyed jointing, particularly benzyl.

If R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ¹⁹' or R ²⁰represent alkylaryl, then it is in particular the C by phenylene keyed jointing ₁-C ₂₀alkyl, such as tolyl or xylyl.

Particularly preferred radicals R ²and/or R ³be selected from following group

Here, group Y representative has 1-20 carbon atom, has the saturated of 1-15 carbon atom or the undersaturated hydrocarbyl group of olefinic especially.Be particularly preferably allyl group, methyl, nonyl, dodecyl as Y or there is the unsaturated C of 1-3 double bond ₁₅alkyl.

Radicals X represents H or alkyl, aryl, aralkyl, is in particular H or methyl.

Index z ' and z " represent numerical value 0,1,2,3,4 or 5, condition is z '+z " summation represent value between 1-5.

Preferably, substituent R ²and R ³identical.

The impelling strength improving agent C3 of formula (XI) is by the polyurethane prepolymer of the straight chain stopped by the individual isocyanate groups of n+n ' or branching and one or more isocyanate-reactive compounds R ²h and/or R ³prepared by H.If use the compound of this isocyanate-reactive multiple, then reaction can in turn or with the mixture of these compounds be carried out.

If substituent R ²and R ³to responding property of epoxy group(ing), then the impelling strength improving agent C3 of formula (XI) is a part of curing agent component K2.If substituent R ²and R ³to responding property of amino, then the impelling strength improving agent C3 of formula (XI) is a part of epoxy resin ingredient K1.If substituent R ²and R ³in room temperature not to responding property of epoxy group(ing) and not to responding property of amino, then the impelling strength improving agent C3 of formula (XI) is a part of epoxy resin ingredient K1 and/or curing agent component K2.The ratio of the impelling strength improving agent C3 of formula (XI) is preferably with 1-45 % by weight, and the amount being in particular 10-30 % by weight uses, based on the weighing scale of respective component K1 and/or K2.

Finally, impelling strength improving agent can be the amino acrylonitrile/butadiene multipolymer C4 stopped in another embodiment, and it is a part of curing agent component K2, and based on the weighing scale of curing agent component K2, it is in particular the amount of 10-40 % by weight.

In a further preferred embodiment, bi-component epoxide-resin composition according to the present invention comprises the combination of the amino impelling strength improving agent C1 of termination and/or the polymkeric substance C3 of fluid rubber C2 and/or formula (XI) and/or the amino acrylonitrile/butadiene multipolymer C4 stopped as impelling strength improving agent C.

Respective component (K1, the weight summation of impelling strength improving agent C1, fluid rubber C2 that the amino existed K2) stops, polymkeric substance C3 and the amino acrylonitrile/butadiene multipolymer C4 stopped preferably no more than 80 % by weight, especially no more than 50 % by weight, based on the weighing scale of respective component (K1, K2).

In one embodiment, at least one core-shell polymer can be comprised further according to bi-component epoxide-resin composition of the present invention.Core-shell polymer is made up of elastic kernel polymkeric substance and rigid crust polymkeric substance.Particularly suitable core-shell polymer is made up of the core of elastic acrylate or butadiene polymer, and this core is wrapped up by the rigid crust of the thermoplastic polymer of rigidity.This nucleocapsid structure is mixed or the spontaneous formation from group by the de-of segmented copolymer, or by designing with the polymerization process of emulsion or suspension polymerization form and grafting subsequently.Preferred core-shell polymer is known as those of MBS polymkeric substance, and it can trade(brand)name Clearstrength ^tMfrom Atofina, Paraloid ^tMfrom Rohm and Haas or F-351 ^tMcommercially available from Zeon.

Particularly preferably using the core shell composite particles that the polymer latex form as drying exists.These example is the GENIOPERL M23A with polysiloxane core and acrylate shell from Wacker, the radiation crosslinking rubber particles of the NEP series of being produced by Eliokem, or from the Nanoprene of Lanxess, or from the Paraloid EXL of Rohm and Haas.

Other comparable core-shell polymer example is by Nanoresins AG(Germany) Albidur that provides ^tM.Core-shell polymer is preferred in epoxy resin ingredient K1.

In one embodiment, at least one filler F can be comprised further according to bi-component epoxide-resin composition of the present invention.It is preferably mica, talcum, kaolin, wollastonite, feldspar, syenite, chlorite, wilkinite, polynite, calcium carbonate (precipitation or grinding), rhombspar, quartz, silicon-dioxide (pyrolysis method or precipitation), cristobalite, calcium oxide, aluminium hydroxide, magnesium oxide, hollow porcelain bead, Hollow Glass Sphere, organic hollow pearl, granulated glass sphere, colored pigment.What term filler F referred to be not only also has uncoated commercially available acquisition and form well known by persons skilled in the art through the filler of organic coat.

Another example is functionalized aikyiaiurnirsoxan beta, such as, at U.S.6,322, in 890 describe those, its content is incorporated herein with entirety.

Based on the weighing scale of whole composition, preferably the total content of whole filler F is 3-50 % by weight, and preferred 5-35 % by weight, is in particular 5-25 % by weight.

The use of filler is favourable, because they improve the resistance to deterioration of tackiness agent and advantageously have impact on mechanical property.

In addition, bi-component epoxide-resin composition can comprise other component.These are such as:

– solvent, film coalescence aid or extender, such as toluene, dimethylbenzene, methylethylketone, cellosolvo, 2-ethoxyethyl acetate, benzylalcohol, ethylene glycol, buiyl diglycol, dipropylene glycol butyl ether, ethylene glycol butyl ether, ethylene glycol phenyl ether, N-Methyl pyrrolidone, propylene glycol butyl ether, propylene glycol phenyl ether, ditan, diisopropylnaphthalene, mineral oil fractions is Solvesso type (deriving from Exxon) such as, aromatic hydrocarbon resin, particularly containing the type of phenolic group, sebate, phthalic ester, organophosphate and sulphonate and sulphonamide,

– reactive diluent, such as those epoxide reaction thinner, epoxy soybean oil or oleum lini as above, there is the polyvalent alcohol of the compound of acetoacetate groups, particularly acetoacetylation, butyrolactone and there is the silicone of isocyanic ester and reactive group in addition;

– polyamine, such as

The primary diamines of aliphatic series, cyclic aliphatic or aryl aliphatic,

Such as ethylene diamine, 1, 2-propylene diamine, 1, 3-propylene diamine, 2-methyl isophthalic acid, 2-propylene diamine, 2, 2-dimethyl-1, 3-propylene diamine, 1, 3-butanediamine, 1, 4-butanediamine, 1, 3-pentamethylene diamine (DAMP), 1, 5-pentamethylene diamine, 1, 5-diamino-2-methylpentane (MPMD), 2-butyl-2-ethyl-1, 5-pentamethylene diamine (the new diamines of C11-), 1, 6-hexanediamine, 2, 5-dimethyl-1, 6-hexanediamine, 2, 2, 4-and 2, 4, 4-trimethylhexamethylenediamine (TMD), 1, 7-heptamethylene diamine, 1, 8-octamethylenediamine, 1, 9-nonamethylene diamine, 1, 10-decamethylene diamine, 1, 11-undecane diamines, 1, 12-dodecamethylene diamine, 1, 2-, 1, 3-and 1, 4-diamino-cyclohexane, two-(4-aminocyclohexyl) methane (H ₁₂-MDA), two-(4-amino-3-methylcyclohexyl) methane, two-(4-amino-3-ethylcyclohexyl) methane, two-(4-amino-3, 5-Dimethylcyclohexyl) methane, two-(4-amino-3-ethyl-5-methylcyclohexyl) methane (M-MECA), 1-amino-3-amino methyl-3, 5, 5-trimethyl-cyclohexane (=isophorone diamine or IPDA), 2-and 4-methyl isophthalic acid, 3-diamino-cyclohexane and its mixture, 1, 3-and 1, 4-pair-(amino methyl) hexanaphthene, 2, 5 (2, 6)-bis--(amino methyl)-dicyclo [2.2.1] heptane (NBDA), 3 (4), 8 (9)-bis--(amino methyl)-three ring [5.2.1.0 ^2,6] decane, Isosorbide-5-Nitrae-diamino-2,2,6-trimethyl-cyclohexane (TMCDA), 1,8-menthane diamines, 3,9-two-(3-aminopropyl)-2,4,8,10-tetra-oxaspiro [5.5] undecane and 1,3-and Isosorbide-5-Nitrae-xylylene amine,

Containing the aliphatic primary diamine of ether,

Such as two (2-amino-ethyl) ether, 3,6-dioxaoctane-1,8-diamines, 4,7-dioxadecane-1,10-diamines, 4,7-dioxadecane-2,9-diamines, 4,9-dioxa dodecane-1,12-diamines, 5,8-dioxa dodecane-3,10-diamines, 4,7,10-trioxatridecane-1, the higher oligomers of 13-diamines and these diamines, two-(3-aminopropyl) polytetrahydrofuran and there are other polytetrahydrofuran diamines of molecular weight of such as 350-2000, and polyoxyalkylene diamines.Generally speaking, the latter is product from the amination of polyoxyalkylene glycol and can such as with title (deriving from Huntsman), with title Polyetheramin (deriving from BASF) or with title PC (deriving from Nitroil) obtains.Specially suitable polyoxyalkylene diamines is d-230, d-400, d-2000, xTJ-511, eD-600, eD-900, eD-2003, xTJ-568, xTJ-569, xTJ-523, xTJ-536, xTJ-542, xTJ-559, eDR-104, eDR-148, eDR-176; Polyetheramin D 230, Polyetheramin D 400 and Polyetheramin D 2000, PC dA 250, PC dA400, PC dA 650 and PC dA 2000;

There is the polyamine of secondary amino group,

Such as diethylenetriamine (DETA), dipropylenetriamine (DPTA), bis hexamethylene triamine (BHMT), 3-(2-amino-ethyl) amino propylamine, N3-(3-Aminopentyl)-1,3-pentamethylene diamine, N5-(3-aminopropyl)-2-methyl isophthalic acid, 5-pentamethylene diamine, N5-(3-amino-1-ethyl propyl)-2-methyl isophthalic acid, 5-pentamethylene diamine, N, N '-dibutyl ethylene diamine; N, N '-di-t-butyl ethylene diamine, N, N '-diethyl-1,6-hexanediamine, 1-(1-methylethylamine)-3-(1-methylethylamine methyl)-3,5,5-trimethyl-cyclohexanes (derive from Huntsman's 754), N4-cyclohexyl-2-methyl-N2-(2-methyl-propyl)-2,4-pentamethylene diamine, N, N '-dialkyl group-1,3-xylylene amine, two-(4-(N-alkylamino) cyclohexyl) methane, 4,4 '-trimethylene two piperidines, N-alkylation polyetheramine, such as type SD-231, SD-401, SD-404 and SD-2001 (deriving from Huntsman);

Amine/polyepoxide adducts,

Particularly by described polyamine and diepoxide with at least 2/1 mol ratio, particularly with the adducts of the mol ratio of 2/1-6/1;

Polyamidoamines amine

It is the reaction product of unitary or polycarboxylic acid or its ester or acid anhydride, the particularly aliphatic series of dimer (fatty acid) yl and stoichiometrically excessive use, cyclic aliphatic or aromatic polyamine, the particularly reaction product of polyalkylene amine such as DETA or Triethylenetetramine (TETA) (TETA), is in particular the polyamidoamines amine of commercially available acquisition 100,125,140 and 150 (deriving from Cognis), 223,250 and 848 (deriving from Huntsman), 3607, 530 (deriving from Huntsman), eH 651, EH 654, EH 655, EH 661 and EH 663 (deriving from Cytec);

Polymine (PEI)

These are the amine of the polymerization of the branching being obtained from polymerization of ethyleneimine.Suitable polymine typically has 250-25, the molecular-weight average of 000g/mol and comprise the amino of uncle, Zhong Hebai.Polymine can such as with trade(brand)name (deriving from BASF) obtains, such as type fG, g20 and pR 8515;

– polymkeric substance such as polymeric amide, polysulphide, polyvinylformal (PVF), polyvinyl butyral (PVB), urethane (PUR), carboxylic polymkeric substance, polymeric amide, perbutan, styrene-acrylonitrile copolymer, butadiene-styrene copolymer, unsaturated monomer is particularly selected from ethene, propylene, butylene, iso-butylene, isoprene, the homopolymer of the monomer of vinyl-acetic ester and (methyl) alkyl acrylate or multipolymer, particularly chlorosulfonated polyethylene and fluoropolymer, the melamine of sulphonamide modified, with the montanin wax of purifying,

– fiber, such as plastics or glass;

– pigment, such as titanium dioxide or ferriferous oxide;

– promotes the promotor reacted between amino and epoxy group(ing), such as acid maybe can be hydrolyzed into the compound of acid, such as organic carboxyl acid is as acetic acid, phenylformic acid, Whitfield's ointment, 2-nitrobenzoic acid, lactic acid, organic sulfonic acid is methanesulfonic, p-toluenesulphonic acids or 4-Witco 1298 Soft Acid such as, sulphonate, other organic or inorganic acid such as phosphoric acid, or the mixture of above-mentioned acid and acid esters; Also has tertiary amine such as 1 in addition, the salt of 4-diazabicyclo [2.2.2] octane, benzyl dimethyl amine, α-methylbenzyl dimethyl amine, trolamine, dimethylamino propylamine, these tertiary amines, quaternary ammonium salt such as benzyl trimethyl ammonium chloride, phenol, particularly bis-phenol, phenol resins and Mannich base be 2-(dimethylaminomethyl) phenol and 2 such as, 4,6-tri--(dimethylaminomethyl) phenol, phosphorous acid ester such as two and triphenyl phosphite, and at the above mentioned compound containing sulfydryl;

– rheology modifier such as particularly thickening material, such as layered silicate is as wilkinite, castor oil derivative, hydrogenated castor oil, polymeric amide, urethane, carbamide compound, pyrogenic silicic acid, ether of cellulose, and hydrophobic modified polyoxyethylene;

– adhesion promotor, such as organic alkoxy decane as 3-glycidoxypropyltrimewasxysilane, 3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-N'-[3-(trimethoxysilyl) propyl group] ethylene diamine, 3-ureido-propyl Trimethoxy silane, 3-r-chloropropyl trimethoxyl silane, vinyltrimethoxy silane, or has the corresponding organosilane of oxyethyl group or (gathering) ether oxygen base replacement methoxyl group;

– is to the stablizer of oxidation, heat, light and UV radiation;

– fire retardant matter, particularly compound be aluminium hydroxide (Al (OH) such as ₃, also referred to as ATH, " aluminum trihydrate "), magnesium hydroxide (Mg (OH) ₂, also referred to as MDH, " two hydrous magnesiums "), ammonium sulfate ((NH ₄) ₂sO ₄), boric acid (B (OH) ₃), zinc borate, melamine borate and melamine cyanurate, phosphorous compound is ammonium phosphate ((NH such as ₄) ₃pO ₄), ammonium polyphosphate, melamine phosphate, melamine pyrophosphate, triphenylphosphate, diphenyl phosphate tolyl ester, lindol, triethyl phosphate, three-(2-ethylhexyl) phosphoric acid ester, trioctyl phosphate, single-, two-and three (isopropyl phenyl) phosphoric acid ester, Resorcinol-bis-(diphenyl phosphate), Resorcinol-bisphosphate oligopolymer, tetraphenyl-Resorcinol diphosphites, ethylene diamine-bisphosphate and dihydroxyphenyl propane-bis-(diphenyl phosphate), halide-containing is chlorine alkyl phosphate such as, particularly three (chloroethyl) phosphoric acid ester, three (chloropropyl) phosphoric acid ester and three (two chloro isopropyls) phosphoric acid ester, many PBDEs, particularly decabromodiphynly oxide, many brominated diphenyls base oxide, three [3-bromo-2, two (brooethyl) propyl group of 2-] phosphoric acid ester, tetrabromo-bisphenol, two (2 of dihydroxyphenyl propane, 3-dibromopropyl ether), brominated epoxy resin, ethylenebis (tetrabromo phthalimide), ethylenebis (dibromo norbornane dicarboximide), 1, 2-pair-(tribromophenoxy) ethane, three (2, 3-dibromopropyl) isocyanuric acid ester, tribromophenol, hexabromocyclododecane, two (hexachlorocyclopentadiene base) cyclooctane, and clorafin, and halide-containing and ANTIMONY TRIOXIDE SB 203 99.8 PCT (Sb ₂o ₃) or antimony pentaoxide (Sb ₂o ₅) combination,

– surfactant, such as wetting agent, flow agent, air release agent or defoamer;

The material of – biocide such as algicide, mycocide or bacteria growing inhibiting.

Those skilled in the art know that and know which component can add epoxy resin ingredient K1 and which can add curing agent component K2.Here, must be noted that especially, stability in storage by these other components influence or only can not affect slightly.Therefore, those skilled in the art are such as very clear, and therefore polyamine will can be only the part of curing agent component with the epoxide reaction in resin Composition.

The weight ratio of epoxy resin ingredient K1 and curing agent component K2 is preferably 4/1-1/1, and especially preferably 2/1.

On the other hand, the present invention relates to the method for adhesive substrate, comprise the following steps:

I) bi-component epoxide-resin composition as defined above is mixed;

Ii) described composition is applied over base material S1, is in particular on metallic surface;

Iii) by the composition epoxy resin that applies and another kind of base material S2, metallic surface contact is in particular; With

Iv) at the temperature of 100 DEG C or lower, preferred 10-40 DEG C, described composition epoxy resin is solidified.

When using as tackiness agent, described composition is applied on base material S1 and/or S2.Therefore can by this adhesive application on a base material or another base material or on two base materials.Engage parts to be bonded subsequently, then tackiness agent is solidified.Here, should notice that being bonded in the so-called unlimited time of parts carries out guaranteeing that two basic change parts are reliably bonded to each other.

Applying of tackiness agent is preferably evenly carried out.

In using at two, base material S1 can be identical or different with base material S2.

The example of suitable base material S1 or S2 be inorganic substrate such as glass, glass-ceramic, concrete, mortar, brick, watt, gypsum and lithotome such as grouan or marble; Particularly metal or alloy such as aluminium, steel, non-ferrous metal, galvanized metal; Organic substrate is timber such as, and plastics are PVC such as, polycarbonate, PMMA, polyester, epoxy resin, the plastics (GFK) of glass fiber reinforcement, carbon fiber reinforced plastics (CFK); The metal or alloy of the base material such as powder coated of coating; And paint and varnish, more especially automobile finish.

To show on the steel that described bi-component epoxide-resin composition adheres to electro-galvanizing particularly well and to have caused the impelling strength that increases.

Importantly realize, effective when not only solidifying at elevated temperatures according to impelling strength improving agent of the present invention, and also they also make impelling strength increase when cured at room temperature.This is apparent anything but, because on the one hand the effect of impelling strength is explained by being separated of setting up period usually, and this is separated and depends on temperature on the other hand.

Preparation is allowed to measure usually to have according to ISO 11343 and at 23 DEG C, be greater than 8.0J and the composition epoxy resin being greater than the energy-to-break of 5.5J at 0 DEG C by described impelling strength improving agent.Usually can prepare there is 9.5J-12J at 23 DEG C and at 0 DEG C the composition of the energy-to-break of 6-9J.

In addition can realize measuring according to ISO 11343 at 23 DEG C, being greater than 20N/mm and the resistance to fracture (shock resistance stripping) being greater than 15N/m at 0 DEG C.Usually can prepare there is 26-30N/mm at 23 DEG C and at 0 DEG C the composition of the breaking tenacity of 18-25N/mm.

If needed, can by base material pre-treatment before applying tackiness agent or sealing agent.This pre-treatment particularly including the cleaning method of physics and/or chemistry, such as grinding, sandblasting, brushing etc., or by sanitising agent or solvent treatment or apply adhesion promotor, adhesion promotion solution or priming paint.

After base material S1 and S2 is by composition bonding according to the present invention or sealing, obtain the goods through bonding.This based article can be Architectural Construction, the more especially Architectural Construction of ground or underground works, or transportation means.Preferably, described goods are transportation means, such as waterborne or land vehicle, particularly automobile, passenger vehicle, truck, train or steamer, or their installation component.Especially preferably, the goods through bonding are transportation means, particularly automobile, or the installation component of transportation means, particularly automobile.

If described composition to be used as in automobile making the tackiness agent bonded, then it preferably has creamlike consistency and structural viscosity performance.This tackiness agent, by means of suitable equipment, is preferably applied on base material with adhesive tape form, and wherein said adhesive tape can have basic circle or leg-of-mutton cross section.Be such as from can manually or the commercially available magazine operated by pressurized air apply for applying the appropriate method of tackiness agent, or apply, optionally by paint robot from bucket or little pail by means of fresh feed pump or forcing machine.There is the tackiness agent well applying performance there is high stability and short wire drawing.This refers to that it keeps the form applied after the application, i.e. not flowing and do not have wire drawing or very short wire drawing after removing the equipment of applying each other, thus not contaminated substrate.

Bonding in automobile making is such as by parts as plastic roof, ornamental strip, flange, collision bumper, wheel house or other installation partss are bonded on the car body of the transportation means of japanning, or bonds glass for vehicle window into car body.As motor vehicle, mention car, truck, passenger vehicle, rail locomotive and steamer.

In preferred embodiments, bi-component epoxide-resin composition is as defined above used as the repairing tackiness agent of two-pack in automobile making.

On the other hand, the invention provides the adhesive article obtained by aforesaid method, and described goods particularly automobile or trolley part.

Embodiment

To provide some embodiments below, it illustrates the present invention further, in any case but do not limit the scope of the invention and some possible embodiments are only described.Table 2 describes compared with prior art according to the experimental evaluation of composition epoxy resin of the present invention.

the preparation method of composition

For being prepared the parent material listed in use table 1.

The parent material that table 1. uses

the amino impelling strength improving agent SM1 stopped

200g Poly-THF 2000,48.18g IPDI and 0.03g dibutyl tin laurate to be weighed in container and to be heated to 80 DEG C under vacuo.The NCO content of 3.5% is recorded after about 120 minutes.Subsequently, the prepolymer P-1 of formation is made to cool 60 minutes under vacuo (to 25 DEG C).Add 234.60g d-2000, and slowly add 70g prepolymer P-1 along with stirring under a nitrogen.Reaction is carried out 60 minutes and so obtains the amino impelling strength improving agent SM1 stopped.NCO group and NH ₂the ratio of group is 0.248.

the amino impelling strength improving agent SM2 stopped

80g Poly-THF 2000,35.18g IPDI and 0.03g dibutyl tin laurate and 80.0g Liquiflex H to be weighed in container and to be heated to 80 DEG C under vacuo.The NCO content of 3.5% is recorded after about 120 minutes.Stir 90 minutes at 80 DEG C in a vacuum and be cooled in other 60 minutes 50 DEG C (=prepolymer P-2) subsequently.By 233.20g d-2000 adds in the second reaction vessel, and slowly adds along with stirring the prepolymer P-2 that 35g is cooled to 35 DEG C during this period in the first reaction vessel.Reaction is carried out 60 minutes and obtains the amino impelling strength improving agent SM2 stopped thus.NCO group and NH ₂the ratio of group is 0.125.

the amino impelling strength improving agent SM3 stopped

50g Poly-THF 2000,33.93g IPDI and 0.02g dibutyl tin laurate to be weighed in container and to be heated to 80 DEG C under vacuo.The NCO content of 4.11% is recorded after about 60 minutes.Add 1g TriMethylolPropane(TMP) subsequently and make it react other 75 minutes under vacuo.Now record the NCO content of 2.60%.In a subsequent step, weigh up 8.70g Hydroxyethyl acrylate (comprising 0.1% quinhydrones) and add above-mentioned reaction mixture at 70 DEG C.Stir at such a temperature under vacuo after 3 hours, from the prepolymer P-3 therefore formed measure 0.55% NCO content.Finally, by 200.30g d-2000 adds in the second reaction vessel, and from the first reaction vessel, slowly adds along with stirring the prepolymer P-3 that (in 60 minutes) 40g is cooled to 25 DEG C during this period under a nitrogen.Reaction is carried out 60 minutes and so obtains the amino impelling strength improving agent SM3 stopped.

the amino impelling strength improving agent SM4 stopped

150g Poly-THF 2000,33.93g IPDI and 0.02g dibutyl tin laurate to be weighed in container and to be heated to 80 DEG C under vacuo.The NCO content of 4.11% is recorded after about 60 minutes.Then add 1g TriMethylolPropane(TMP) and make reaction carry out other 75 minutes under vacuo, and recording the NCO content of 2.60%.

In a subsequent step, weigh up 8.70g Hydroxyethyl acrylate (comprising 0.1% quinhydrones) and add above-mentioned reaction mixture at 70 DEG C.Stir at such a temperature under vacuo after 3 hours, from the prepolymer P-4 therefore formed measure 0.55% NCO content.Finally, by 100.1g d-400 adds the second reaction vessel, and from the first reaction vessel, slowly add the prepolymer P-4 that (in 60 minutes, along with stirring) 100g is cooled to 25 DEG C during this period.Make reaction carry out 60 minutes and obtain the amino impelling strength improving agent SM4 stopped.

the amino impelling strength improving agent SM5 stopped

By 80.00g Poly-THF 2000,30.53g IPDI and 0.02g dibutyl tin laurate and 80g 7250 to be weighed in container and to be heated to 80 DEG C under vacuo.NCO content (3.00%) is measured after about 120 minutes.In 60 minutes, make the polymer P-5 formed thus be cooled to 20 DEG C.Finally, by 201.20g d-2000 adds in the second reaction vessel, and from the first reaction vessel, slowly add the prepolymer P-5 that (in 60 minutes, along with stirring) 35g is cooled to 25 DEG C.Make reaction carry out 60 minutes and obtain the amino impelling strength improving agent SM5 stopped.NCO group and NH ₂the ratio of group is 0.063.

the amino impelling strength improving agent SM6 stopped

By 210.0g 7490,27.81g IPDI and 0.03g dibutyl tin laurate to be weighed in container and to be heated to 80 DEG C under vacuo.NCO content (2.60%) (=prepolymer P-6) is measured after 120 minutes.Finally, by 146.20g d-2000 adds in the second reaction vessel, and from the first reaction vessel, slowly add the prepolymer P-6 that (in 60 minutes, along with stirring) 40g is cooled to 25 DEG C during this period.Make reaction carry out 60 minutes and obtain the amino impelling strength improving agent SM6 stopped.NCO group and NH ₂the ratio of group is 0.085.

the amino impelling strength improving agent SM7 stopped

By 220g 4200N, 27.4g IPDI and 0.01g dibutyl tin laurate to be weighed in container and to heat under vacuo.The NCO content of 2.25% is recorded after about 2 hours.By the polymer P-7 that formed thus, (=(=prepolymer P-7) is cooled to 20 DEG C.Finally, by 69.8g Jeffamin-D400-tert-butyl acrylate ( d-400 and tert-butyl acrylate, the reaction product of ratio 1:0.8) add second container, and slowly add (in 60 minutes) 40g prepolymer P-7.Make reaction carry out 60 minutes and obtain the amino impelling strength improving agent SM7 stopped.

the preparation of impelling strength improving agent C3-1

By 150g 2000 (OH value 57mg/g KOH, BASF) and 150gLiquiflex H (OH value 46mg/g KOH, Krahn) at 105 DEG C dry 30 minutes under vacuo.After temperature is down to 90 DEG C, add 64.0g isophorone diisocyanate and 0.13g dibutyl tin laurate.At 90 DEG C, continue reaction under vacuo until obtained after 2.5 hours constant 3.30% NCO content (the NCO content of calculating: 3.38%).Subsequently, 103.0g encapsulant is added nC-700 (Cardanol, Cardolite).Continue under vacuo to stir until NCO content drops to less than 0.1% after 3.5 hr at 105 DEG C.The urethane impact modifiers called after C3-1 closed formed thus.

Two-component composition described in preparation table 2.Weight part for the numeral described in component in table 2.In the preparation process of corresponding resin or curing agent component, at 40 DEG C, corresponding liquid ingredient is added stirred vessel and blended solid material and stirring under applying vacuum condition under agitation at 23 DEG C subsequently.The resin formed or curing agent component have creamlike consistency and to load in tinned(sheet)iron tank and to seal.

Table 2. two-component composition (data are with parts by weight).

First composition: the mixture ratio=2:1 (w:w) of the second composition.

¹toughner B=is according to [0075] section preparation in US 2005/0070634 A1; ²dynasilan A187 (epoxy radicals silicone hydride, Evonik); ³lupasol P (BASF)=polymine, Mw=750,000g/mol, in water 50%; ⁴lupasolWF (BASF)=polymine, Mw=25,000g/mol); ⁵catalyzer=2,4,6-tri-(dimethylaminomethyl) phenol

Comparative example Ref.1 is can from the commercially available tackiness agent Betamate of Dow Automotive ^tM2096.Comparative example Ref.2 is the example " tackiness agent example 1 " be made up of the component " A1 " of the prior art described in WO 2009/025991 and " B1 ".The component " A1 " that comparative example Ref.3 corresponds to prior art described in WO 2009/025991 and the example that the curing agent component " B1 " of filling mixes with the weight ratio of 2:1.Comparative example Ref.4 corresponds to for according to the resin Composition of embodiments of the invention 1-6 and the combination of curing agent component " B1 " of filling being described in the prior art in WO 2009/025991.Comparative example Ref.5 corresponds to the combination for mixing with the 2:1 weight ratio of the curing agent component through filling of the curing agent component " B1 " be adjusted in WO 2009/025991 according to the resin Composition of embodiments of the invention 1-6, described curing agent component has the Versamid of 30 % by weight ratios, according to the claim 1 of WO 2009/025991, this is for the higher limit disclosed in polymeric amide (Versamid).Comparative example Ref.6 corresponds to for according to the resin Composition of embodiments of the invention 1-6 and the combination mixed by 2:1 weight ratio of the curing agent component through filling of curing agent component " B1 " being adjusted to WO2009/025991, described curing agent component has the Versamid of 10 % by weight ratios, according to the claim 1 of WO 2009/025991, this is for the lower value disclosed in polymeric amide (Versamid).

Testing method:

In order to test, use stirrer by the corresponding resin of table 2 and curing agent component with the resin Composition of 2:1: curing agent component weight ratio mixes each other substantially equably, and is directly applied on the substrate surface for the preparation of sample body.

tensile shear strength (ZSF) (DIN EN 1465)

Sample is prepared by described example composition and with the DC04 steel (eloZn) of size 100 × 25 × 1.5mm of electrogalvanizing.Bond front acetone and clean base material.Bond area is 25x10mm, and thickness is 0.3mm.Solidify after 7 days at 23 DEG C, under the rate of extension of 10mm/min, at room temperature measure tensile shear strength (ZSF _{7d, RT}).Result is summarized in table 3.

impact peel merit (ISO 11343)

Sample is prepared by described example composition and with the DC04 steel (eloZn) of size 90 × 20 × 0.8mm of electrogalvanizing, is 20 × 30mm and thickness 0.3mm at this adhesive face.Solidify 7 days at 23 DEG C.Each comfortable 23 DEG C of (BE _rT) under and at 0 DEG C of (BE _{0 ° of C}) under carry out the measurement of impact peel merit.Impact speed is 2m/s.As energy-to-break (the BE) (BE pressing Joulemeter _rTor BE _{0 ° of C}), report be area (from 25% to 90%, according to ISO 11343) under experiment curv.Impact peel strength value (impact peel) according to ISO 11343 at 23 DEG C of (IP _rT) under and at 0 DEG C of (IP _{0 ° of C}) under measure.Result is summarized in table 3.

result

The mechanical property of the composition that table 3. solidifies

As can be seen from Table 3, compared with composition 1-6 according to the present invention, comparative example Ref.1 to Ref.6 has significantly lower resistance to impact shock (energy-to-break & impact peel strength) on the steel of electro-galvanizing.On the contrary, composition 1-6 according to the present invention has those 10 times the impact peel strength values being better than the comparative example corresponding to prior art compositions.Although tensile shear strength reduces slightly, they still have height and acceptable level.The result of table 2 shows the Beneficial Effect of the combination of the special and amino impelling strength improving agent stopped of polyamide of reduction.

Even if comprise filler according in composition of the present invention, also can be compensated more (comparing between 1 with Ref.2) owing to using the reduction (comparison between Ref.2 and Ref.3) of the energy-to-break that causes of filler or impact peel strength.

Due to the snappiness increased, composition according to the present invention has the remarkable increase of energy-to-break.Therefore, even if adhering junction also can not be ruptured under higher impact load, but there is enough snappinesies to keep their bonding integrity completely.But, the composition of comparative example due to snappiness significantly lower so that adhering junction is ruptured under comparatively underload.

Therefore, even if be particularly suitable for wherein requiring that adhering junction under circumstances of high mechanical loads according to impelling strength improving agent of the present invention and the composition epoxy resin comprising it, such as, in accident situation, the automobile making of their integrity is also kept.

Claims

1. bi-component epoxide-resin composition, comprises:

-comprising the epoxy resin ingredient K1 of at least one epoxy resin A, described epoxy resin A per molecule comprises on average more than one epoxy group(ing);

With

-curing agent component K2, it comprises the polymeric amide B that the amino based on the total weight 1-10 % by weight of curing agent component stops;

Wherein at least one of component K1, K2 comprises at least one impelling strength improving agent C,

Described impelling strength improving agent C is selected from the impelling strength improving agent C1 that polyurethane prepolymer by making to have isocyanate groups, primary diamines and amino that optionally prepared by least one Michael receptor response stop, the polyurethane prepolymer wherein with isocyanate groups is had polyester polyol or the polyether glycol preparation of at least two hydroxyls by least one polyisocyanates and at least one, and described impelling strength improving agent C1 is a part of curing agent component K2

The polymkeric substance C3 of formula (XI),

Wherein R ¹it is the polyurethane prepolymer of the straight chain stopped by the individual isocyanate groups of n+n ' after removing all terminal isocyanate group group or branching;

R ²and R ³be selected from the substituting group by the following group formed independently of one another separately

With---O-R ²⁸

Wherein R ¹⁴it itself is the group of the aliphatic series comprising uncle or secondary hydroxyl, cyclic aliphatic, aromatics or the araliphatic epoxide after removing hydroxyl or epoxy group(ing);

Pp represents numerical value 1,2 or 3;

R ¹⁵, R ¹⁶, R ¹⁷and R ¹⁸alkyl or cycloalkyl or aromatic alkyl group independently of one another separately;

Or

R ¹⁵with R ¹⁶together, or R ¹⁷with R ¹⁸form a part for optional 4 to 7 rings replaced together;

R ¹⁹, R ^{19 '}and R ²⁰separately alkyl or aromatic alkyl group independently of one another, or alkoxyl group or aryloxy or aralkoxy;

R ²¹represent alkyl;

R ²³and R ²⁴the alkylidene group with 2-5 carbon atom optionally comprising double bond or be substituted independently of one another separately, or the phenylene of phenylene or hydrogenation;

R ²⁵, R ²⁶and R ²⁷separately H or alkyl or aryl or aromatic alkyl group independently of one another;

R ²⁸it is that aralkyl or the monokaryon optionally with aromatic hydroxy or multinuclear replace or unsubstituted aromatic compound moieties;

And the value of n and n ' each 0-7 naturally independently of one another, the value of condition to be n+n ' be 1-8,

Or its combination.

2. bi-component epoxide-resin composition according to claim 1, is characterised in that the impelling strength improving agent C1 that described amino stops has formula (II)

Wherein

And R ⁵be selected from by-COOR ⁷,-CONH ₂,-CONHR ⁷,-CONR ⁷ ₂,-CN ,-NO ₂,-PO (OR ⁷) ₂,-SO ₂r ⁷with-SO ₂(OR ⁷) group of group that forms, and

Wherein R ⁷it is the monovalent hydrocarbon group with 1-20 carbon atom;

Y ⁵it is the divalent group of formula (IV) or (IV ');

Wherein

R ^{4 '}be hydrogen atom or be selected from by-R ⁷,-COOR ⁷the group of the group that He – CN forms,

R ^{5 '}be selected from by-COOR ⁷,-CONH ₂,-CONHR ⁷,-CONR ⁷ ₂,-CN ,-NO ₂,-PO (OR ⁷) ₂,-SO ₂r ⁷with-SO ₂(OR ⁷) group of group that forms, and

R ^{6 '}be hydrogen atom or be selected from by-R ⁷,-COOR ⁷,-CH ₂cOOR ⁷the group of the group that He – CN forms,

Wherein R ⁷it is the monovalent hydrocarbon group with 1-20 carbon atom;

P and p ' is 0 or 1 separately;

Q and q ' is 0 or 1 separately;

M and m ' is the value of 0-7 separately, and condition is the value that m+m ' is 1-8.

3., according to the bi-component epoxide-resin composition of aforementioned claim 1, be characterised in that described composition comprises the fluid rubber C2 of the polymkeric substance stopped containing epoxy in addition as impelling strength improving agent,

And described fluid rubber C2 is a part of epoxy resin ingredient K1.

4. according to the bi-component epoxide-resin composition of aforementioned claim 1, be characterised in that described composition comprises the amino acrylonitrile/butadiene multipolymer C4 stopped in addition as impelling strength improving agent, and described acrylonitrile/butadiene multipolymer C4 is a part of curing agent component K2.

5. bi-component epoxide-resin composition according to claim 1, be characterised in that described composition comprises the polymkeric substance C3 of the amino impelling strength improving agent C1 that stops and/or formula (XI), and the combination of acrylonitrile/butadiene multipolymer C4 that the amino of definition in the fluid rubber C2 of definition in optional claim 3 and/or claim 4 stops is as impelling strength improving agent C

With---O-R ²⁸

Pp represents numerical value 1,2 or 3;

Or

R ²¹represent alkyl;

And the value of n and n ' each 0-7 naturally independently of one another, the value of condition to be n+n ' be 1-8.

6. bi-component epoxide-resin composition according to claim 5, be characterised in that at respective component (K1, the weight summation no more than 80 % by weight of impelling strength improving agent C1, fluid rubber C2 that the amino existed K2) stops, polymkeric substance C3 and the amino acrylonitrile/butadiene multipolymer C4 stopped, based on the weighing scale of respective component (K1, K2).

7., according to the bi-component epoxide-resin composition of aforementioned claim 1, be characterised in that described curing agent component K2 comprises poly-(ethyleneimine) of at the most 20 % by weight in addition, based on the total weight of curing agent component.

8., according to the bi-component epoxide-resin composition of aforementioned claim 1, be characterised in that described composition comprises at least one filler F in addition.

9., according to the bi-component epoxide-resin composition of aforementioned claim 1, be characterised in that the weight ratio of epoxy resin ingredient K1 and curing agent component K2 is 4/1 to 1/1.

10., according to the bi-component epoxide-resin composition of aforementioned claim 1, be characterised in that the polymeric amide B that described amino stops is the lipid acid of dimerization and the reaction product of polyamines.

11., according to the bi-component epoxide-resin composition of aforementioned claim 1, are characterised in that, described curing agent component K2 comprises the polymeric amide B that the amino based on the total weight 4-8 % by weight of curing agent component stops.

12., according to the bi-component epoxide-resin composition of aforementioned claim 1, are characterised in that, the impelling strength improving agent C1 that described amino stops is present in curing agent component K2 with the amount of the weighing scale 1-30 % by weight based on curing agent component K2.

13. according to the bi-component epoxide-resin composition of aforementioned claim 2, and be characterised in that, m and m ' is 0 or 1 or 2 separately.

14. according to the bi-component epoxide-resin composition of aforementioned claim 2, and be characterised in that, m+m ' is 1 or 2.

15., according to the bi-component epoxide-resin composition of aforementioned claim 3, are characterised in that, described fluid rubber C2 comprises the acrylonitrile/butadiene multipolymer that epoxy stops.

16. according to the bi-component epoxide-resin composition of aforementioned claim 3, and be characterised in that, described fluid rubber C2 is present in epoxy resin ingredient K1 with the amount of the weighing scale 1-45 % by weight based on epoxy resin ingredient K1.

17. according to the bi-component epoxide-resin composition of aforementioned claim 1, and be characterised in that, n and n ' is 0 or 1 or 2 separately.

18. according to the bi-component epoxide-resin composition of aforementioned claim 1, and be characterised in that, n+n ' is 1 or 2.

19., according to the bi-component epoxide-resin composition of aforementioned claim 4, are characterised in that, the acrylonitrile/butadiene multipolymer C4 that described amino stops is present in curing agent component K2 with the amount of the weighing scale 10-40 % by weight based on curing agent component K2.

20. according to the bi-component epoxide-resin composition of aforementioned claim 5, and be characterised in that, n and n ' is 0 or 1 or 2 separately.

21. according to the bi-component epoxide-resin composition of aforementioned claim 5, and be characterised in that, n+n ' is 1 or 2.

22. according to the bi-component epoxide-resin composition of aforementioned claim 6, be characterised in that, the weight summation no more than 50 % by weight of impelling strength improving agent C1, fluid rubber C2 that described amino stops, polymkeric substance C3 and the amino acrylonitrile/butadiene multipolymer C4 stopped, based on the weighing scale of respective component (K1, K2).

23. according to the bi-component epoxide-resin composition of aforementioned claim 8, and be characterised in that, the amount of described filler is the weighing scale 3-50 % by weight based on described composition.

24. according to the bi-component epoxide-resin composition of aforementioned claim 9, and be characterised in that, the weight ratio of described epoxy resin ingredient K1 and curing agent component K2 is 2/1.

The method of 25. adhesive substrate, comprises the following steps:

I) mixing is according to the bi-component epoxide-resin composition of any one of claim 1-24;

Ii) described composition is applied on the surface of base material S1;

Iii) by the surface contact of the composition epoxy resin that applies and another kind of base material S2; With

Iv) under 140 DEG C or lower temperature, described composition epoxy resin is solidified.

26. methods according to claim 25, is characterized in that, at step I v) in be solidificated in the temperature of 10-60 DEG C under carry out.

27. methods according to claim 25, is characterized in that, described base material S1 is metal.

28. methods according to claim 25, is characterized in that, described base material S2 is metal.

29. keep in repair the purposes of tackiness agent according to the bi-component epoxide-resin composition of any one of claim 1-24 in Rail car manufacture as two-pack.

30. adhesive articles by obtaining according to the method for any one of claim 25 to 28.

31. adhesive articles according to claim 30, is characterized in that, described adhesive article is vehicle or vehicle part.